CN104437624A - Vinyl acetate catalyst and preparation method thereof and vinyl acetate synthesis method - Google Patents
Vinyl acetate catalyst and preparation method thereof and vinyl acetate synthesis method Download PDFInfo
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- CN104437624A CN104437624A CN201310435312.0A CN201310435312A CN104437624A CN 104437624 A CN104437624 A CN 104437624A CN 201310435312 A CN201310435312 A CN 201310435312A CN 104437624 A CN104437624 A CN 104437624A
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Abstract
The invention relates to a catalyst for synthesizing vinyl acetate through an ethylene method and a preparation method of the catalyst, mainly aiming at solving problem that a catalyst in the prior art is low in space time yield and selectivity. The catalyst comprises active ingredients, an auxiliary catalyst and a carrier, wherein the active ingredients include Pd, Au and an alloy thereof, the auxiliary catalyst is potassium acetate, the content of Pd in the catalyst is 1.0-12g/L, the content of Au is 0.1-9.0g/L, and the content of the auxiliary catalyst is 10-50g/l. The catalyst is characterized in that the carrier of the catalyst is SiO2 modified by a fluorinated compound. The problem is well solved through the catalyst, and the catalyst can be applied to industrial production of vinyl acetate synthesis through the ethylene method.
Description
Technical field
The present invention relates to the preparation method of ethene vapor phase method vinyl acetate catalyst, this catalyst, and the synthetic method of vinyl acetate.
Background technology
Vinylacetate, be called for short vinyl acetate (VAM), it is one of maximum Organic Chemicals of world wide production, be widely used in producing a series of chemical products such as polyvinyl acetate, polyvinyl alcohol, coating, slurry, adhesive, polyvinyl, film, vinyl copolymer resin, acetal resin, its application is also in continuous expansion.
A method for vinyl acetate is prepared in the industry known, and refers to that ethene, acetic acid and oxygen are under Supported Pd-Catalyst exists, and are realized by gas-phase reaction.
A kind of preferred vinyl acetate catalyst is as SiO at its carrier mass
2, Al
2o
3or on the surface of its compound, a certain amount of Pd metal of load and Au metal.
Be used for the standard method of the vinyl acetate catalyst prepared containing dispersion Pd and Au on a catalyst support, comprise: (1) is with a kind of solution impregnating carrier of water miscible Pd and Au compound; (2) catalyst carrier through flooding by contacting with a kind of alkaline aqueous solution that can react with water miscible Pd with Au compound, thus forms the metallic compound being insoluble in water, is also fixed on a catalyst support by water-fast Pd and Au compound precipitation; (3) wash treated catalyst with water, precipitating to remove; (4) processing with reducing agent, is by the initial anion discharged in Pd and the Au compound of dipping in journey by water-fast Pd and Au converting compounds, and free metallic state; Final step is nonessential, it usually containing (5) with the catalyst of a kind of alkali-metal alkaline solution dipping through reduction, drier obtained finished catalyst;
The activity and selectivity of loading type Pd-Au catalyst, by the Material Form of Pd and Au in catalyst carrier, the impact of tenor.Several important relevant vinyl acetate Kaolinite Preparation of Catalyst and preparation method thereof is discussed below.
Nineteen sixty-five, US Patent No. 3190912(title: Process for preparing esters) disclose the preparation method of the catalyst for the preparation of unsaturated organic ester, wherein catalyst is made up of non-loading type or support type platinum family or palladium race metal or its oxide or its organic salt or inorganic salts.Loaded catalyst is prepared by following steps: slaine is soluble in water; Add carrier; Solvent evaporated.Noble metal is evenly distributed on whole carrier.
1966, Bayer company of Germany discloses (US3275680, title: Production of organic acetates in presence of a noble metal catalyst and oxygen) a kind of load Pd catalyst on the alumina support, when finding to use alkali metal acetate as co-catalyst, this catalyst is applicable to prepare organic acid ester, particularly vinylacetate.In this patent, Pd catalyst with above-mentioned patent the same by uniform deposition in whole catalyst carrier.Difference is, in catalyst preparation process, after the solution impregnating carrier of precious metal salt, adding reduction step is that noble metal loading is on carrier.
Knapsack company (US3743607, title: Palladium-gold catalyst) discloses a kind of containing Pd and Au bimetallic catalyst, and colleague also added alkali metal acetate as co-catalyst.This method for preparing catalyst is as follows: the solution impregnating carrier using Pd salt and Au salt, as silicic acid, aluminium oxide, silicate or aluminum phosphate etc.; The mixture of generation is evaporated to dry.With reducing agent, Pd salt and Au salt are reverted to metallic state.Then catalyst is washed with water, by SAS dipping also drying for standby.
1973, Japan Patent (48-10135/1973) disclosed a kind of method preparing the support type vinyl acetate catalyst of surface impregnation.In Vehicle element, be deposited on whole porous carrier by a small amount of reducing metal (as Au), flood the Pd catalyst of requirement subsequently, it is deposited on around prefabricated surface of metal particles.Pd catalyst deposit is superficial layer, and its thickness is about 15% or thinner of particle radius.Alkali metal acetate is recommended to be used as co-catalyst.
1977, Du pont company of the U.S. discloses (US4048096, title: Surface impregnated catalyst) a kind of preparation method of vinyl acetate catalyst, Pd and Au bimetallic active component selected by this catalyst, and alkali metal acetate is co-catalyst.Adopt the incipient impregnation precipitation method, by being stirred by carrier machinery in a rotary container, the slaine of dissolving being adsorbed onto on carrier from the solution equaling pore volume, then under not dry load has the condition of the carrier of salt, with alkali, these salt being fixed.The finished catalyst of gained belongs to " eggshell type " catalyst, and surface layer thickness is only 0.5 mm.Succeeding in developing of this catalyst makes the performance of ethylene process vinyl acetate catalyst significantly be promoted.The catalyst formulation used in current industrial ethylene process vinyl acetate production is almost identical with above-mentioned catalyst with preparation technology.But this catalyst catalyst activity, selective etc. in still have the space of lifting.
Summary of the invention
One of technical problem to be solved by this invention is the catalyst space-time yield and selective low problem that exist in prior art, provides a kind of new vinyl acetate catalyst, and this catalyst has space time yield and selective high feature.
Technical problem two to be solved by this invention, is to provide the preparation method of the corresponding catalyst of one of a kind of and above-mentioned technical problem.
Technical problem three to be solved by this invention, is to provide a kind of synthetic method adopting the vinyl acetate of the described catalyst of one of above-mentioned technical problem.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: for the catalyst of ethylene process vinyl acetate synthesis, described active component is Pd, Au and alloy thereof, co-catalyst is potassium acetate, in wherein said catalyst, Pd content is 1.0-12 g/L, Au content is 0.1-9.0 g/L, and described cocatalyst content is 10 ~ 50 g/L; The carrier of described catalyst is a kind of SiO of fluorochemical modification
2.
In catalyst described in technique scheme, Oil repellent is preferably 0.5 ~ 5.0 g/L; Described fluorochemical is preferably at least one in the salt of hydrofluoric acid and hydrofluoric acid, fluosilicate, the mixture that the salt being more preferably hydrofluoric acid and hydrofluoric acid forms; The salt of described hydrofluoric acid is preferably at least one in the alkali metal salt of the ammonium salt of hydrofluoric acid, hydrofluoric acid; The alkali metal salt of described hydrofluoric acid is preferably at least one in NaF, KF; 1 is preferably: (0.1 ~ 10) with the salt of hydrofluoric acid described in the molar ratio computing of fluorine element and the ratio of hydrofluoric acid; Described carrier B ET specific area is preferably 150 ~ 200 cm
2/ g, pore volume is preferably 0.6 ~ 0.8 cm
3/ g.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: the as mentioned above preparation method of catalyst, comprises the following steps:
A aequum water-soluble fluorine-containing compound is dissolved in the aqueous solution and makes maceration extract A by (), adopt infusion process, the carrier silica gel of aequum and maceration extract are mixed to get precursor carrier I;
B () is dry by precursor carrier I, obtain precursor carrier II;
C precursor carrier II is obtained carrier III after roasting by () under air atmosphere condition;
D aequum palladium, gold compound are dissolved in solvent and make maceration extract B by (), the carrier III of aequum and maceration extract B is mixed to get catalyst precarsor I;
E aequum alkali metal silicate solutions mixes with above-mentioned catalyst precarsor I by () makes described palladium, gold compound is converted into sedimentation type, obtains catalyst precarsor II;
F (), by reducing agent reducing catalyst precursor II, obtains catalyst precarsor III;
G the co-catalyst potassium acetate of aequum is dissolved in pure water and makes maceration extract C by (), mixed by the catalyst precarsor III of aequum with maceration extract C, and drying dewaters to obtain described catalyst.
In technique scheme, described in (a) step, infusion process preferably adopts equi-volume impregnating; In technique scheme, the temperature of step (b) drying is preferably 60 ~ 120 DEG C, and the temperature of step (c) roasting is preferably 200 ~ 500 DEG C; D the palladium compound described in () step can be palladium bichloride (II), sodium chloride palladium (II), potassium chloride palladium (II), palladium nitrate (II) or palladium sulfate (II), described gold compound can be the alkali metal salt of chlorauride (III) or tetrachloro gold (III) acid such as-sodium salt or-sylvite; E alkali silicate described in () step can be the K of the silicate of sodium or potassium, described silicate
2o/SiO
2mol ratio or Na
2o/SiO
2mol ratio is not particularly limited, obtain alkali metal silicate solutions as long as can dissolve all can reach object of the present invention with water, can be such as alkali-metal metasilicate, alkali-metal orthosilicate, can also to be modulus be 1 ~ 3 KP1 or sodium silicate; About (f) step, one skilled in the art will appreciate that, if when remaining containing Na in catalyst precarsor III, the performance being reduced the step catalyst of the present invention of wherein Na content by washing precursor II I is more excellent.
For solve the problems of the technologies described above three, the technical solution used in the present invention is as follows: the method for vinyl acetate synthesis, under catalyst described in any one of one of technical problem technical scheme exists, oxygen is consisted of: ethene: nitrogen: acetic acid=1: 5 ~ 7: 4 ~ 8: 1 ~ 2 with molar ratio computing raw material, reaction pressure is 6.0 ~ 8.0 atm, reaction temperature is 130 ~ 200 DEG C, and raw material volume air speed is 1600 ~ 3000 h
-1.
Reaction pressure of the present invention is gauge pressure.
Select Pd and Au as active component with prior art, potassium acetate is as co-catalyst load SiO
2carrier obtains vinyl acetate catalyst and compares, and the present invention selects fluorochemical to carrier S iO
2carried out modification, F atom part replaces Silica Surface-OH group, forms Si-F group, and then improves the catalyst space-time yield and selective of knowing clearly.Further, when the present invention selects the salt mixture of hydrofluoric acid and hydrofluoric acid as co-catalyst, improve catalyst space-time yield and selective in effect more obvious, there is synergy, and this synergy is selecting NH
4f and HF is to SiO
2the most obvious when carrying out modification.Experimental result shows, reaction pressure is 7.0 atm, reaction temperature 150 DEG C, feed gas volume air speed 2000 h
-1reacting gas consists of oxygen: ethene: nitrogen: acetic acid=1: when 5.25: 5: 1.2, the space time yield of catalyst of the present invention brings up to 842 grams per liters hour by 638 grams per liters hour of prior art catalyst, selectively improves 4.8%, achieves good technique effect.
Detailed description of the invention
[embodiment 1]
(1) carrier S iO
2pre-treatment
A () gets containing NH
4the aqueous solution 800 ml of F is maceration extract A(F ion concentration: 3.0 g/L), floods preparing spherical SiO 2 carrier (BET specific surface 175 cm that 1000 ml diameters are 5.8 mm
2/ g, pore volume is 0.7 cm
3/ g) 3hr obtains catalyst precarsor I;
(b) by above-mentioned precursor carrier I in air dry oven, 105
ounder C condition, dry 4 hr obtain precursor carrier II;
C precursor carrier II is placed in Muffle furnace by (), in air atmosphere 400
ounder C condition, roasting 3hr obtains carrier III;
(2) catalyst preparing
A () gets containing H
2pdCl
4and HAuCl
4the aqueous solution 800 ml be maceration extract B(palladium content: 2.75 g/L, gold content: 0.625 g/L), dipping 1000ml carrier III 3 hr obtains catalyst precarsor I;
B () is by 27.5g Na
2siO
39H
2o is made into the 100 ml aqueous solution and is added in above-mentioned catalyst precarsor I, and shake is for several times to avoid caking, and after leaving standstill 24 hr, under 80 DEG C of conditions, dry 8 hr obtain catalyst precarsor II;
C () in nitrogen atmosphere, (flow velocity is 0.2 ml/min, and temperature is 150 by catalyst precarsor II
oc) be down to room temperature after reductase 12 hr in and obtain catalyst precarsor III;
D () gets containing the KOAc aqueous solution 450 ml is maceration extract (KOAc:0.1 g/ml), and impregnated catalyst precursor II I 3 hr, in 105
ounder C condition, dry 6 hr obtain finished catalyst;
The main preparation condition of catalyst lists in table 1.
(3) physical property characterizes
Inductively coupled plasma spectrum generator (ICP) is used to measure Pd, Au, K content in finished catalyst.In catalyst, F constituent content is by solid-state nuclear magnetic resonance F spectrometry.
The physical property of catalyst lists in table 2.
(4) catalyst performance evaluation
Use fixed bed reactors evaluation, actual conditions is:
Catalyst packing volume: 700 ml;
Reaction raw materials composition (in mole hundred parts of ratios): oxygen: ethene: nitrogen: acetic acid=1:5.25:5:1.2;
Raw material volume air speed: 2000 hr
-1;
Reaction pressure: 7.0 atm;
Reaction temperature: 150
oc;
Reaction time: 500 hr;
With the content of each component in gas chromatography analytical reactions product, then calculate the space time yield of catalyst and selective.
Table 2 lists space time yield and the selective data of catalyst.
[embodiment 2]
(1) carrier S iO
2pre-treatment
A () gets containing (NH
4)
3siF
6the aqueous solution 800 ml be maceration extract A(F ion concentration: 3.0 g/L), flood preparing spherical SiO 2 carrier (BET specific surface 175 cm that 1000 ml diameters are 5.8 mm
2/ g, pore volume is 0.7 cm
3/ g) 3hr obtains catalyst precarsor I;
(b) by above-mentioned precursor carrier I in air dry oven, 105
ounder C condition, dry 4 hr obtain precursor carrier II;
C precursor carrier II is placed in Muffle furnace by (), in air atmosphere 400
ounder C condition, roasting 3 hr obtains carrier III;
(2) catalyst preparing
A () gets containing H
2pdCl
4and HAuCl
4aqueous solution 800ml be maceration extract B(palladium content: 2.75 g/L, gold content: 0.625 g/L), dipping 1000ml carrier III 3 hr obtains catalyst precarsor I;
B () is by 27.5g Na
2siO
39H
2o is made into the 100 ml aqueous solution and is added in above-mentioned catalyst precarsor I, and shake is for several times to avoid caking, and after leaving standstill 24 hr, under 80 DEG C of conditions, dry 8 hr obtain catalyst precarsor II;
C () at hydrogen atmosphere, (flow velocity is 0.2 ml/min, and temperature is 150 by catalyst precarsor II
oc) be down to room temperature after reductase 12 hr in and obtain catalyst precarsor III;
D () gets containing the KOAc aqueous solution 450 ml is maceration extract (KOAc:0.1 g/ml), and impregnated catalyst precursor II I 3 hr, in 105
ounder C condition, dry 6 hr obtain finished catalyst;
The main preparation condition of catalyst lists in table 1.
(3) physical property characterizes
Use inductively coupled plasma spectrum generator (ICP) to measure Pd, Au, K content in finished catalyst, in catalyst, F constituent content is by solid-state nuclear magnetic resonance F spectrometry.The physical property of catalyst lists in table 2.
(4) catalyst performance evaluation
Use fixed bed reactors evaluation, actual conditions is:
Catalyst packing volume: 700 ml;
Reaction raw materials composition (in mole hundred parts of ratios): oxygen: ethene: nitrogen: acetic acid=1:5.25:5:1.2;
Raw material volume air speed: 2000 hr
-1;
Reaction pressure: 7.0 atm;
Reaction temperature: 150
oc;
Reaction time: 500 hr;
With the content of each component in gas chromatography analytical reactions product, then calculate the space time yield of catalyst and selective.
Table 2 lists space time yield and the selective data of catalyst.
[embodiment 3]
(1) carrier S iO
2pre-treatment
A the () aqueous solution 800 ml got containing NaF is maceration extract A(F ion concentration: 3.0 g/L), flood preparing spherical SiO 2 carrier (BET specific surface 175 cm that 1000 ml diameters are 5.8 mm
2/ g, pore volume is 0.7 cm
3/ g) 3hr obtains catalyst precarsor I;
(b) by above-mentioned precursor carrier I in air dry oven, 105
ounder C condition, dry 4 hr obtain precursor carrier II;
C precursor carrier II is placed in Muffle furnace by (), in air atmosphere 400
ounder C condition, roasting 3 hr obtains carrier III;
(2) catalyst preparing
A () gets containing H
2pdCl
4and HAuCl
4aqueous solution 800ml be maceration extract B(palladium content: 2.75 g/L, gold content: 0.625 g/L), dipping 1000ml carrier III 3 hr obtains catalyst precarsor I;
B () is by 27.5g Na
2siO
39H
2o is made into the 100 ml aqueous solution and is added in above-mentioned catalyst precarsor I, and shake is for several times to avoid caking, and after leaving standstill 24 hr, under 80 DEG C of conditions, dry 8 hr obtain catalyst precarsor II;
C () at hydrogen atmosphere, (flow velocity is 0.2 ml/min, and temperature is 150 by catalyst precarsor II
oc) be down to room temperature after reductase 12 hr in and obtain catalyst precarsor III;
D () gets containing the KOAc aqueous solution 450 ml is maceration extract (KOAc:0.1 g/ml), and impregnated catalyst precursor II I 3 hr, in 105
ounder C condition, dry 6 hr obtain finished catalyst;
The main preparation condition of catalyst lists in table 1.
(3) physical property characterizes
Use inductively coupled plasma spectrum generator (ICP) to measure Pd, Au, K content in finished catalyst, in catalyst, F constituent content is by solid-state nuclear magnetic resonance F spectrometry.The physical property of catalyst lists in table 2.
(4) catalyst performance evaluation
Use fixed bed reactors evaluation, actual conditions is:
Catalyst packing volume: 700 ml;
Reaction raw materials composition (in mole hundred parts of ratios): oxygen: ethene: nitrogen: acetic acid=1:5.25:5:1.2;
Raw material volume air speed: 2000 hr
-1;
Reaction pressure: 7.0 atm;
Reaction temperature: 150
oc;
Reaction time: 500 hr;
With the content of each component in gas chromatography analytical reactions product, then calculate the space time yield of catalyst and selective.
Table 2 lists space time yield and the selective data of catalyst.
[embodiment 4]
(1) carrier S iO
2pre-treatment
A the () aqueous solution 800 ml got containing KF is maceration extract A(F ion concentration: 3.0 g/L), flood preparing spherical SiO 2 carrier (BET specific surface 175 cm that 1000 ml diameters are 5.8 mm
2/ g, pore volume is 0.7 cm
3/ g) 3hr obtains catalyst precarsor I;
(b) by above-mentioned precursor carrier I in air dry oven, 105
ounder C condition, dry 4 hr obtain precursor carrier II;
C precursor carrier II is placed in Muffle furnace by (), in air atmosphere 400
ounder C condition, roasting 3 hr obtains carrier III;
(2) catalyst preparing
A () gets containing H
2pdCl
4and HAuCl
4aqueous solution 800ml be maceration extract B(palladium content: 2.75 g/L, gold content: 0.625 g/L), dipping 1000ml carrier III 3 hr obtains catalyst precarsor I;
B () is by 27.5g Na
2siO
39H
2o is made into the 100 ml aqueous solution and is added in above-mentioned catalyst precarsor I, and shake is for several times to avoid caking, and after leaving standstill 24 hr, under 80 DEG C of conditions, dry 8 hr obtain catalyst precarsor II;
C () at hydrogen atmosphere, (flow velocity is 0.2 ml/min, and temperature is 150 by catalyst precarsor II
oc) be down to room temperature after reductase 12 hr in and obtain catalyst precarsor III;
D () gets containing the KOAc aqueous solution 450 ml is maceration extract (KOAc:0.1 g/ml), and impregnated catalyst precursor II I 3 hr, in 105
ounder C condition, dry 6 hr obtain finished catalyst;
The main preparation condition of catalyst lists in table 1.
(3) physical property characterizes
Use inductively coupled plasma spectrum generator (ICP) to measure Pd, Au, K content in finished catalyst, in catalyst, F constituent content is by solid-state nuclear magnetic resonance F spectrometry.The physical property of catalyst lists in table 2.
(4) catalyst performance evaluation
Use fixed bed reactors evaluation, actual conditions is:
Catalyst packing volume: 700 ml;
Reaction raw materials composition (in mole hundred parts of ratios): oxygen: ethene: nitrogen: acetic acid=1:5.25:5:1.2;
Raw material volume air speed: 2000 hr
-1;
Reaction pressure: 7.0 atm;
Reaction temperature: 150
oc;
Reaction time: 500 hr;
With the content of each component in gas chromatography analytical reactions product, then calculate the space time yield of catalyst and selective.
Table 2 lists space time yield and the selective data of catalyst.
[embodiment 5]
(1) carrier S iO
2pre-treatment
A () gets containing NH
4f and HF mixed aqueous solution (n
f (NH4F): n
f (HF)=1: 0.5) 800 ml are maceration extract A(F ion concentration: 3.0 g/L), flood preparing spherical SiO 2 carrier (BET specific surface 175 cm that 1000 ml diameters are 5.8 mm
2/ g, pore volume is 0.7 cm
3/ g) 3hr obtains catalyst precarsor I;
(b) by above-mentioned precursor carrier I in air dry oven, 105
ounder C condition, dry 4 hr obtain precursor carrier II;
C precursor carrier II is placed in Muffle furnace by (), in air atmosphere 400
ounder C condition, roasting 3 hr obtains carrier III;
(2) catalyst preparing
A () gets containing H
2pdCl
4and HAuCl
4aqueous solution 800ml be maceration extract B(palladium content: 2.75 g/L, gold content: 0.625 g/L), dipping 1000ml carrier III 3 hr obtains catalyst precarsor I;
B () is by 27.5g Na
2siO
39H
2o is made into the 100 ml aqueous solution and is added in above-mentioned catalyst precarsor I, and shake is for several times to avoid caking, and after leaving standstill 24 hr, under 80 DEG C of conditions, dry 8 hr obtain catalyst precarsor II;
C () at hydrogen atmosphere, (flow velocity is 0.2 ml/min, and temperature is 150 by catalyst precarsor II
oc) be down to room temperature after reductase 12 hr in and obtain catalyst precarsor III;
D () gets containing the KOAc aqueous solution 450 ml is maceration extract (KOAc:0.1 g/ml), and impregnated catalyst precursor II I 3 hr, in 105
ounder C condition, dry 6 hr obtain finished catalyst;
The main preparation condition of catalyst lists in table 1.
(3) physical property characterizes
Use inductively coupled plasma spectrum generator (ICP) to measure Pd, Au, K content in finished catalyst, in catalyst, F constituent content is by solid-state nuclear magnetic resonance F spectrometry.The physical property of catalyst lists in table 2.
(4) catalyst performance evaluation
Use fixed bed reactors evaluation, actual conditions is:
Catalyst packing volume: 700 ml;
Reaction raw materials composition (in mole hundred parts of ratios): oxygen: ethene: nitrogen: acetic acid=1:5.25:5:1.2;
Raw material volume air speed: 2000 hr
-1;
Reaction pressure: 7.0 atm;
Reaction temperature: 150
oc;
Reaction time: 500 hr;
With the content of each component in gas chromatography analytical reactions product, then calculate the space time yield of catalyst and selective.
Table 2 lists space time yield and the selective data of catalyst.
[embodiment 6]
(1) carrier S iO
2pre-treatment
A () gets containing NH
4f and HF mixed aqueous solution (n
f (NH4F): n
f (HF)=1: 1) 800 ml are maceration extract A(F ion concentration: 3.0 g/L), flood preparing spherical SiO 2 carrier (BET specific surface 175 cm that 1000 ml diameters are 5.8 mm
2/ g, pore volume is 0.7 cm
3/ g) 3hr obtains catalyst precarsor I;
(b) by above-mentioned precursor carrier I in air dry oven, 105
ounder C condition, dry 4 hr obtain precursor carrier II;
C precursor carrier II is placed in Muffle furnace by (), in air atmosphere 400
ounder C condition, roasting 3 hr obtains carrier III;
(2) catalyst preparing
A () gets containing H
2pdCl
4and HAuCl
4aqueous solution 800ml be maceration extract B(palladium content: 2.75 g/L, gold content: 0.625 g/L), dipping 1000ml carrier III 3 hr obtains catalyst precarsor I;
B () is by 27.5g Na
2siO
39H
2o is made into the 100 ml aqueous solution and is added in above-mentioned catalyst precarsor I, and shake is for several times to avoid caking, and after leaving standstill 24 hr, under 80 DEG C of conditions, dry 8 hr obtain catalyst precarsor II;
C () at hydrogen atmosphere, (flow velocity is 0.2 ml/min, and temperature is 150 by catalyst precarsor II
oc) be down to room temperature after reductase 12 hr in and obtain catalyst precarsor III;
D () gets containing the KOAc aqueous solution 450 ml is maceration extract (KOAc:0.1 g/ml), and impregnated catalyst precursor II I 3 hr, in 105
ounder C condition, dry 6 hr obtain finished catalyst;
The main preparation condition of catalyst lists in table 1.
(3) physical property characterizes
Use inductively coupled plasma spectrum generator (ICP) to measure Pd, Au, K content in finished catalyst, in catalyst, F constituent content is by solid-state nuclear magnetic resonance F spectrometry.The physical property of catalyst lists in table 2.
(4) catalyst performance evaluation
Use fixed bed reactors evaluation, actual conditions is:
Catalyst packing volume: 700 ml;
Reaction raw materials composition (in mole hundred parts of ratios): oxygen: ethene: nitrogen: acetic acid=1:5.25:5:1.2;
Raw material volume air speed: 2000 hr
-1;
Reaction pressure: 7.0 atm;
Reaction temperature: 150
oc;
Reaction time: 500 hr;
With the content of each component in gas chromatography analytical reactions product, then calculate the space time yield of catalyst and selective.
Table 2 lists space time yield and the selective data of catalyst.
[embodiment 7]
(1) carrier S iO
2pre-treatment
A () gets containing NH
4f and HF mixed aqueous solution (n
f (NH4F): n
f (HF)=1: 2) 800 ml are maceration extract A(F ion concentration: 3.0 g/L), flood preparing spherical SiO 2 carrier (BET specific surface 175 cm that 1000 ml diameters are 5.8 mm
2/ g, pore volume is 0.7 cm
3/ g) 3hr obtains catalyst precarsor I;
(b) by above-mentioned precursor carrier I in air dry oven, 105
ounder C condition, dry 4 hr obtain precursor carrier II;
C precursor carrier II is placed in Muffle furnace by (), in air atmosphere 400
ounder C condition, roasting 3 hr obtains carrier III;
(2) catalyst preparing
A () gets containing H
2pdCl
4and HAuCl
4aqueous solution 800ml be maceration extract B(palladium content: 2.75 g/L, gold content: 0.625 g/L), dipping 1000ml carrier III 3 hr obtains catalyst precarsor I;
B () is by 27.5g Na
2siO
39H
2o is made into the 100 ml aqueous solution and is added in above-mentioned catalyst precarsor I, and shake is for several times to avoid caking, and after leaving standstill 24 hr, under 80 DEG C of conditions, dry 8 hr obtain catalyst precarsor II;
C () at hydrogen atmosphere, (flow velocity is 0.2 ml/min, and temperature is 150 by catalyst precarsor II
oc) be down to room temperature after reductase 12 hr in and obtain catalyst precarsor III;
D () gets containing the KOAc aqueous solution 450 ml is maceration extract (KOAc:0.1 g/ml), and impregnated catalyst precursor II I 3 hr, in 105
ounder C condition, dry 6 hr obtain finished catalyst;
The main preparation condition of catalyst lists in table 1.
(3) physical property characterizes
Use inductively coupled plasma spectrum generator (ICP) to measure Pd, Au, K content in finished catalyst, in catalyst, F constituent content is by solid-state nuclear magnetic resonance F spectrometry.The physical property of catalyst lists in table 2.
(4) catalyst performance evaluation
Use fixed bed reactors evaluation, actual conditions is:
Catalyst packing volume: 700 ml;
Reaction raw materials composition (in mole hundred parts of ratios): oxygen: ethene: nitrogen: acetic acid=1:5.25:5:1.2;
Raw material volume air speed: 2000 hr
-1;
Reaction pressure: 7.0 atm;
Reaction temperature: 150
oc;
Reaction time: 500 hr;
With the content of each component in gas chromatography analytical reactions product, then calculate the space time yield of catalyst and selective.
Table 2 lists space time yield and the selective data of catalyst.
[embodiment 8]
(1) carrier S iO
2pre-treatment
A () gets containing NH
4f and HF mixed aqueous solution (n
f (NH4F): n
f (HF)=1: 3) 800 ml are maceration extract A(F ion concentration: 3.0 g/L), flood preparing spherical SiO 2 carrier (BET specific surface 175 cm that 1000 ml diameters are 5.8 mm
2/ g, pore volume is 0.7 cm
3/ g) 3hr obtains catalyst precarsor I;
(b) by above-mentioned precursor carrier I in air dry oven, 105
ounder C condition, dry 4 hr obtain precursor carrier II;
C precursor carrier II is placed in Muffle furnace by (), in air atmosphere 400
ounder C condition, roasting 3 hr obtains carrier III;
(2) catalyst preparing
A () gets containing H
2pdCl
4and HAuCl
4aqueous solution 800ml be maceration extract B(palladium content: 2.75 g/L, gold content: 0.625 g/L), dipping 1000ml carrier III 3 hr obtains catalyst precarsor I;
B () is by 27.5g Na
2siO
39H
2o is made into the 100 ml aqueous solution and is added in above-mentioned catalyst precarsor I, and shake is for several times to avoid caking, and after leaving standstill 24 hr, under 80 DEG C of conditions, dry 8 hr obtain catalyst precarsor II;
C () at hydrogen atmosphere, (flow velocity is 0.2 ml/min, and temperature is 150 by catalyst precarsor II
oc) be down to room temperature after reductase 12 hr in and obtain catalyst precarsor III;
D () gets containing the KOAc aqueous solution 450 ml is maceration extract (KOAc:0.1 g/ml), and impregnated catalyst precursor II I 3 hr, in 105
ounder C condition, dry 6 hr obtain finished catalyst;
The main preparation condition of catalyst lists in table 1.
(3) physical property characterizes
Use inductively coupled plasma spectrum generator (ICP) to measure Pd, Au, K content in finished catalyst, in catalyst, F constituent content is by solid-state nuclear magnetic resonance F spectrometry.The physical property of catalyst lists in table 2.
(4) catalyst performance evaluation
Use fixed bed reactors evaluation, actual conditions is:
Catalyst packing volume: 700 ml;
Reaction raw materials composition (in mole hundred parts of ratios): oxygen: ethene: nitrogen: acetic acid=1:5.25:5:1.2;
Raw material volume air speed: 2000 hr
-1;
Reaction pressure: 7.0 atm;
Reaction temperature: 150
oc;
Reaction time: 500 hr;
With the content of each component in gas chromatography analytical reactions product, then calculate the space time yield of catalyst and selective.
Table 2 lists space time yield and the selective data of catalyst.
[embodiment 9]
(1) carrier S iO
2pre-treatment
A () gets containing NH
4f and HF mixed aqueous solution (n
f (NH4F): n
f (HF)=1: 4) 800 ml are maceration extract A(F ion concentration: 3.0 g/L), flood preparing spherical SiO 2 carrier (BET specific surface 175 cm that 1000 ml diameters are 5.8 mm
2/ g, pore volume is 0.7 cm
3/ g) 3hr obtains catalyst precarsor I;
(b) by above-mentioned precursor carrier I in air dry oven, 105
ounder C condition, dry 4 hr obtain precursor carrier II;
C precursor carrier II is placed in Muffle furnace by (), in air atmosphere 400
ounder C condition, roasting 3 hr obtains carrier III;
(2) catalyst preparing
A () gets containing H
2pdCl
4and HAuCl
4aqueous solution 800ml be maceration extract B(palladium content: 2.75 g/L, gold content: 0.625 g/L), dipping 1000ml carrier III 3 hr obtains catalyst precarsor I;
B () is by 27.5g Na
2siO
39H
2o is made into the 100 ml aqueous solution and is added in above-mentioned catalyst precarsor I, and shake is for several times to avoid caking, and after leaving standstill 24 hr, under 80 DEG C of conditions, dry 8 hr obtain catalyst precarsor II;
C () at hydrogen atmosphere, (flow velocity is 0.2 ml/min, and temperature is 150 by catalyst precarsor II
oc) be down to room temperature after reductase 12 hr in and obtain catalyst precarsor III;
D () gets containing the KOAc aqueous solution 450 ml is maceration extract (KOAc:0.1 g/ml), and impregnated catalyst precursor II I 3 hr, in 105
ounder C condition, dry 6 hr obtain finished catalyst;
The main preparation condition of catalyst lists in table 1.
(3) physical property characterizes
Use inductively coupled plasma spectrum generator (ICP) to measure Pd, Au, K content in finished catalyst, in catalyst, F constituent content is by solid-state nuclear magnetic resonance F spectrometry.The physical property of catalyst lists in table 2.
(4) catalyst performance evaluation
Use fixed bed reactors evaluation, actual conditions is:
Catalyst packing volume: 700 ml;
Reaction raw materials composition (in mole hundred parts of ratios): oxygen: ethene: nitrogen: acetic acid=1:5.25:5:1.2;
Raw material volume air speed: 2000 hr
-1;
Reaction pressure: 7.0 atm;
Reaction temperature: 150
oc;
Reaction time: 500 hr;
With the content of each component in gas chromatography analytical reactions product, then calculate the space time yield of catalyst and selective.
Table 2 lists space time yield and the selective data of catalyst.
[embodiment 10]
(1) carrier S iO
2pre-treatment
A () gets containing NH
4f and HF mixed aqueous solution (n
f (NH4F): n
f (HF)=1: 5) 800 ml are maceration extract A(F ion concentration: 3.0 g/L), flood preparing spherical SiO 2 carrier (BET specific surface 175 cm that 1000 ml diameters are 5.8 mm
2/ g, pore volume is 0.7 cm
3/ g) 3hr obtains catalyst precarsor I;
(b) by above-mentioned precursor carrier I in air dry oven, 105
ounder C condition, dry 4 hr obtain precursor carrier II;
C precursor carrier II is placed in Muffle furnace by (), in air atmosphere 400
ounder C condition, roasting 3 hr obtains carrier III;
(2) catalyst preparing
A () gets containing H
2pdCl
4and HAuCl
4aqueous solution 800ml be maceration extract B(palladium content: 2.75 g/L, gold content: 0.625 g/L), dipping 1000ml carrier III 3 hr obtains catalyst precarsor I;
B () is by 27.5g Na
2siO
39H
2o is made into the 100 ml aqueous solution and is added in above-mentioned catalyst precarsor I, and shake is for several times to avoid caking, and after leaving standstill 24 hr, under 80 DEG C of conditions, dry 8 hr obtain catalyst precarsor II;
C () at hydrogen atmosphere, (flow velocity is 0.2 ml/min, and temperature is 150 by catalyst precarsor II
oc) be down to room temperature after reductase 12 hr in and obtain catalyst precarsor III;
D () gets containing the KOAc aqueous solution 450 ml is maceration extract (KOAc:0.1 g/ml), and impregnated catalyst precursor II I 3 hr, in 105
ounder C condition, dry 6 hr obtain finished catalyst;
The main preparation condition of catalyst lists in table 1.
(3) physical property characterizes
Use inductively coupled plasma spectrum generator (ICP) to measure Pd, Au, K content in finished catalyst, in catalyst, F constituent content is by solid-state nuclear magnetic resonance F spectrometry.The physical property of catalyst lists in table 2.
(4) catalyst performance evaluation
Use fixed bed reactors evaluation, actual conditions is:
Catalyst packing volume: 700 ml;
Reaction raw materials composition (in mole hundred parts of ratios): oxygen: ethene: nitrogen: acetic acid=1:5.25:5:1.2;
Raw material volume air speed: 2000 hr
-1;
Reaction pressure: 7.0 atm;
Reaction temperature: 150
oc;
Reaction time: 500 hr;
With the content of each component in gas chromatography analytical reactions product, then calculate the space time yield of catalyst and selective.
Table 2 lists space time yield and the selective data of catalyst.
[embodiment 11]
(1) carrier S iO
2pre-treatment
A () gets containing (NH
4)
3siF
6with HF mixed aqueous solution (n
f ((NH4) 3SiF6): n
f (HF)=1: 3) 800 ml are maceration extract A(F ion concentration: 3.0 g/L), flood preparing spherical SiO 2 carrier (BET specific surface 175 cm that 1000 ml diameters are 5.8 mm
2/ g, pore volume is 0.7 cm
3/ g) 3hr obtains catalyst precarsor I;
(b) by above-mentioned precursor carrier I in air dry oven, 105
ounder C condition, dry 4 hr obtain precursor carrier II;
C precursor carrier II is placed in Muffle furnace by (), in air atmosphere 400
ounder C condition, roasting 3 hr obtains carrier III;
(2) catalyst preparing
A () gets containing H
2pdCl
4and HAuCl
4aqueous solution 800ml be maceration extract B(palladium content: 2.75 g/L, gold content: 0.625 g/L), dipping 1000ml carrier III 3 hr obtains catalyst precarsor I;
B () is by 27.5g Na
2siO
39H
2o is made into the 100 ml aqueous solution and is added in above-mentioned catalyst precarsor I, and shake is for several times to avoid caking, and after leaving standstill 24 hr, under 80 DEG C of conditions, dry 8 hr obtain catalyst precarsor II;
C () at hydrogen atmosphere, (flow velocity is 0.2 ml/min, and temperature is 150 by catalyst precarsor II
oc) be down to room temperature after reductase 12 hr in and obtain catalyst precarsor III;
D () gets containing the KOAc aqueous solution 450 ml is maceration extract (KOAc:0.1 g/ml), and impregnated catalyst precursor II I 3 hr, in 105
ounder C condition, dry 6 hr obtain finished catalyst;
The main preparation condition of catalyst lists in table 1.
(3) physical property characterizes
Use inductively coupled plasma spectrum generator (ICP) to measure Pd, Au, K content in finished catalyst, in catalyst, F constituent content is by solid-state nuclear magnetic resonance F spectrometry.The physical property of catalyst lists in table 2.
(4) catalyst performance evaluation
Use fixed bed reactors evaluation, actual conditions is:
Catalyst packing volume: 700 ml;
Reaction raw materials composition (in mole hundred parts of ratios): oxygen: ethene: nitrogen: acetic acid=1:5.25:5:1.2;
Raw material volume air speed: 2000 hr
-1;
Reaction pressure: 7.0 atm;
Reaction temperature: 150
oc;
Reaction time: 500 hr;
With the content of each component in gas chromatography analytical reactions product, then calculate the space time yield of catalyst and selective.
Table 2 lists space time yield and the selective data of catalyst.
[embodiment 12]
(1) carrier S iO
2pre-treatment
A () gets containing NaF and HF mixed aqueous solution (n
f (NaF): n
f (HF)=1: 3) 800 ml are maceration extract A(F ion concentration: 3.0 g/L), flood preparing spherical SiO 2 carrier (BET specific surface 175 cm that 1000 ml diameters are 5.8 mm
2/ g, pore volume is 0.7 cm
3/ g) 3hr obtains catalyst precarsor I;
(b) by above-mentioned precursor carrier I in air dry oven, 105
ounder C condition, dry 4 hr obtain precursor carrier II;
C precursor carrier II is placed in Muffle furnace by (), in air atmosphere 400
ounder C condition, roasting 3 hr obtains carrier III;
(2) catalyst preparing
A () gets containing H
2pdCl
4and HAuCl
4aqueous solution 800ml be maceration extract B(palladium content: 2.75 g/L, gold content: 0.625 g/L), dipping 1000ml carrier III 3 hr obtains catalyst precarsor I;
B () is by 27.5g Na
2siO
39H
2o is made into the 100 ml aqueous solution and is added in above-mentioned catalyst precarsor I, and shake is for several times to avoid caking, and after leaving standstill 24 hr, under 80 DEG C of conditions, dry 8 hr obtain catalyst precarsor II;
C () at hydrogen atmosphere, (flow velocity is 0.2 ml/min, and temperature is 150 by catalyst precarsor II
oc) be down to room temperature after reductase 12 hr in and obtain catalyst precarsor III;
D () gets containing the KOAc aqueous solution 450 ml is maceration extract (KOAc:0.1 g/ml), and impregnated catalyst precursor II I 3 hr, in 105
ounder C condition, dry 6 hr obtain finished catalyst;
The main preparation condition of catalyst lists in table 1.
(3) physical property characterizes
Use inductively coupled plasma spectrum generator (ICP) to measure Pd, Au, K content in finished catalyst, in catalyst, F constituent content is by solid-state nuclear magnetic resonance F spectrometry.The physical property of catalyst lists in table 2.
(4) catalyst performance evaluation
Use fixed bed reactors evaluation, actual conditions is:
Catalyst packing volume: 700 ml;
Reaction raw materials composition (in mole hundred parts of ratios): oxygen: ethene: nitrogen: acetic acid=1:5.25:5:1.2;
Raw material volume air speed: 2000 hr
-1;
Reaction pressure: 7.0 atm;
Reaction temperature: 150
oc;
Reaction time: 500 hr;
With the content of each component in gas chromatography analytical reactions product, then calculate the space time yield of catalyst and selective.
Table 2 lists space time yield and the selective data of catalyst.
[embodiment 13]
(1) carrier S iO
2pre-treatment
A () gets containing KF and HF mixed aqueous solution (n
f (KF): n
f (HF)=1: 3) 800 ml are maceration extract A(F ion concentration: 3.0 g/L), flood preparing spherical SiO 2 carrier (BET specific surface 175 cm that 1000 ml diameters are 5.8 mm
2/ g, pore volume is 0.7 cm
3/ g) 3hr obtains catalyst precarsor I;
(b) by above-mentioned precursor carrier I in air dry oven, 105
ounder C condition, dry 4 hr obtain precursor carrier II;
C precursor carrier II is placed in Muffle furnace by (), in air atmosphere 400
ounder C condition, roasting 3 hr obtains carrier III;
(2) catalyst preparing
A () gets containing H
2pdCl
4and HAuCl
4aqueous solution 800ml be maceration extract B(palladium content: 2.75 g/L, gold content: 0.625 g/L), dipping 1000ml carrier III 3 hr obtains catalyst precarsor I;
B () is by 27.5g Na
2siO
39H
2o is made into the 100 ml aqueous solution and is added in above-mentioned catalyst precarsor I, and shake is for several times to avoid caking, and after leaving standstill 24 hr, under 80 DEG C of conditions, dry 8 hr obtain catalyst precarsor II;
C () at hydrogen atmosphere, (flow velocity is 0.2 ml/min, and temperature is 150 by catalyst precarsor II
oc) be down to room temperature after reductase 12 hr in and obtain catalyst precarsor III;
D () gets containing the KOAc aqueous solution 450 ml is maceration extract (KOAc:0.1 g/ml), and impregnated catalyst precursor II I 3 hr, in 105
ounder C condition, dry 6 hr obtain finished catalyst;
The main preparation condition of catalyst lists in table 1.
(3) physical property characterizes
Use inductively coupled plasma spectrum generator (ICP) to measure Pd, Au, K content in finished catalyst, in catalyst, F constituent content is by solid-state nuclear magnetic resonance F spectrometry.The physical property of catalyst lists in table 2.
(4) catalyst performance evaluation
Use fixed bed reactors evaluation, actual conditions is:
Catalyst packing volume: 700 ml;
Reaction raw materials composition (in mole hundred parts of ratios): oxygen: ethene: nitrogen: acetic acid=1:5.25:5:1.2;
Raw material volume air speed: 2000 hr
-1;
Reaction pressure: 7.0 atm;
Reaction temperature: 150
oc;
Reaction time: 500 hr;
With the content of each component in gas chromatography analytical reactions product, then calculate the space time yield of catalyst and selective.
Table 2 lists space time yield and the selective data of catalyst.
[embodiment 14]
(1) carrier S iO
2pre-treatment
A () gets containing NH
4f and HF mixed aqueous solution (n
f (NH4F): n
f (HF)=1: 3) 800 ml are maceration extract A(F ion concentration: 3.0 g/L), flood preparing spherical SiO 2 carrier (BET specific surface 175 cm that 1000 ml diameters are 5.8 mm
2/ g, pore volume is 0.7 cm
3/ g) 3hr obtains catalyst precarsor I;
(b) by above-mentioned precursor carrier I in air dry oven, 105
ounder C condition, dry 4 hr obtain precursor carrier II;
C precursor carrier II is placed in Muffle furnace by (), in air atmosphere 400
ounder C condition, roasting 3 hr obtains carrier III;
(2) catalyst preparing
A () gets containing H
2pdCl
4and HAuCl
4aqueous solution 800ml be maceration extract B(palladium content: 2.75 g/L, gold content: 0.625 g/L), dipping 1000ml carrier III 3 hr obtains catalyst precarsor I;
B () is by 27.5g Na
2siO
39H
2o is made into the 100 ml aqueous solution and is added in above-mentioned catalyst precarsor I, and shake is for several times to avoid caking, and after leaving standstill 24 hr, under 80 DEG C of conditions, dry 8 hr obtain catalyst precarsor II;
C () at hydrogen atmosphere, (flow velocity is 0.2 ml/min, and temperature is 150 by catalyst precarsor II
oc) be down to room temperature after reductase 12 hr in and obtain catalyst precarsor III;
D () gets containing the KOAc aqueous solution 450 ml is maceration extract (KOAc:0.1 g/ml), and impregnated catalyst precursor II I 3 hr, in 105
ounder C condition, dry 6 hr obtain finished catalyst;
The main preparation condition of catalyst lists in table 1.
(3) physical property characterizes
Use inductively coupled plasma spectrum generator (ICP) to measure Pd, Au, K content in finished catalyst, in catalyst, F constituent content is by solid-state nuclear magnetic resonance F spectrometry.The physical property of catalyst lists in table 2.
(4) catalyst performance evaluation
Use fixed bed reactors evaluation, actual conditions is:
Catalyst packing volume: 700 ml;
Reaction raw materials composition (in mole hundred parts of ratios): oxygen: ethene: nitrogen: acetic acid=1:5:4:1;
Raw material volume air speed: 1600 hr
-1;
Reaction pressure: 6.0 atm;
Reaction temperature: 130
oc;
Reaction time: 500 hr;
With the content of each component in gas chromatography analytical reactions product, then calculate the space time yield of catalyst and selective.
Table 2 lists space time yield and the selective data of catalyst.
[embodiment 15]
(1) carrier S iO
2pre-treatment
A () gets containing NH
4f and HF mixed aqueous solution (n
f (NH4F): n
f (HF)=1: 3) 800 ml are maceration extract A(F ion concentration: 3.0 g/L), flood preparing spherical SiO 2 carrier (BET specific surface 175 cm that 1000 ml diameters are 5.8 mm
2/ g, pore volume is 0.7 cm
3/ g) 3hr obtains catalyst precarsor I;
(b) by above-mentioned precursor carrier I in air dry oven, 105
ounder C condition, dry 4 hr obtain precursor carrier II;
C precursor carrier II is placed in Muffle furnace by (), in air atmosphere 400
ounder C condition, roasting 3 hr obtains carrier III;
(2) catalyst preparing
A () gets containing H
2pdCl
4and HAuCl
4aqueous solution 800ml be maceration extract B(palladium content: 2.75 g/L, gold content: 0.625 g/L), dipping 1000ml carrier III 3 hr obtains catalyst precarsor I;
B () is by 27.5g Na
2siO
39H
2o is made into the 100 ml aqueous solution and is added in above-mentioned catalyst precarsor I, and shake is for several times to avoid caking, and after leaving standstill 24 hr, under 80 DEG C of conditions, dry 8 hr obtain catalyst precarsor II;
C () at hydrogen atmosphere, (flow velocity is 0.2 ml/min, and temperature is 150 by catalyst precarsor II
oc) be down to room temperature after reductase 12 hr in and obtain catalyst precarsor III;
D () gets containing the KOAc aqueous solution 450 ml is maceration extract (KOAc:0.1 g/ml), and impregnated catalyst precursor II I 3 hr, in 105
ounder C condition, dry 6 hr obtain finished catalyst;
The main preparation condition of catalyst lists in table 1.
(3) physical property characterizes
Use inductively coupled plasma spectrum generator (ICP) to measure Pd, Au, K content in finished catalyst, in catalyst, F constituent content is by solid-state nuclear magnetic resonance F spectrometry.The physical property of catalyst lists in table 2.
(4) catalyst performance evaluation
Use fixed bed reactors evaluation, actual conditions is:
Catalyst packing volume: 700 ml;
Reaction raw materials composition (in mole hundred parts of ratios): oxygen: ethene: nitrogen: acetic acid=1:5:4:1;
Raw material volume air speed: 2400 hr
-1;
Reaction pressure: 6.5 atm;
Reaction temperature: 165
oc;
Reaction time: 500 hr;
With the content of each component in gas chromatography analytical reactions product, then calculate the space time yield of catalyst and selective.
Table 2 lists space time yield and the selective data of catalyst.
[embodiment 16]
(1) carrier S iO
2pre-treatment
A () gets containing NH
4f and HF mixed aqueous solution (n
f (NH4F): n
f (HF)=1: 3) 800 ml are maceration extract A(F ion concentration: 3.0 g/L), flood preparing spherical SiO 2 carrier (BET specific surface 175 cm that 1000 ml diameters are 5.8 mm
2/ g, pore volume is 0.7 cm
3/ g) 3hr obtains catalyst precarsor I;
(b) by above-mentioned precursor carrier I in air dry oven, 105
ounder C condition, dry 4 hr obtain precursor carrier II;
C precursor carrier II is placed in Muffle furnace by (), in air atmosphere 400
ounder C condition, roasting 3 hr obtains carrier III;
(2) catalyst preparing
A () gets containing H
2pdCl
4and HAuCl
4aqueous solution 800ml be maceration extract B(palladium content: 2.75 g/L, gold content: 0.625 g/L), dipping 1000ml carrier III 3 hr obtains catalyst precarsor I;
B () is by 27.5g Na
2siO
39H
2o is made into the 100 ml aqueous solution and is added in above-mentioned catalyst precarsor I, and shake is for several times to avoid caking, and after leaving standstill 24 hr, under 80 DEG C of conditions, dry 8 hr obtain catalyst precarsor II;
C () at hydrogen atmosphere, (flow velocity is 0.2 ml/min, and temperature is 150 by catalyst precarsor II
oc) be down to room temperature after reductase 12 hr in and obtain catalyst precarsor III;
D () gets containing the KOAc aqueous solution 450 ml is maceration extract (KOAc:0.1 g/ml), and impregnated catalyst precursor II I 3 hr, in 105
ounder C condition, dry 6 hr obtain finished catalyst;
The main preparation condition of catalyst lists in table 1.
(3) physical property characterizes
Use inductively coupled plasma spectrum generator (ICP) to measure Pd, Au, K content in finished catalyst, in catalyst, F constituent content is by solid-state nuclear magnetic resonance F spectrometry.The physical property of catalyst lists in table 2.
(4) catalyst performance evaluation
Use fixed bed reactors evaluation, actual conditions is:
Catalyst packing volume: 700 ml;
Reaction raw materials composition (in mole hundred parts of ratios): oxygen: ethene: nitrogen: acetic acid=1:7:8:2;
Raw material volume air speed: 2700 hr
-1;
Reaction pressure: 7.5 atm;
Reaction temperature: 180
oc;
Reaction time: 500 hr;
With the content of each component in gas chromatography analytical reactions product, then calculate the space time yield of catalyst and selective.
Table 2 lists space time yield and the selective data of catalyst.
[embodiment 17]
(1) carrier S iO
2pre-treatment
A () gets containing NH
4f and HF mixed aqueous solution (n
f (NH4F): n
f (HF)=1: 3) 800 ml are maceration extract A(F ion concentration: 3.0 g/L), flood preparing spherical SiO 2 carrier (BET specific surface 175 cm that 1000 ml diameters are 5.8 mm
2/ g, pore volume is 0.7 cm
3/ g) 3hr obtains catalyst precarsor I;
(b) by above-mentioned precursor carrier I in air dry oven, 105
ounder C condition, dry 4 hr obtain precursor carrier II;
C precursor carrier II is placed in Muffle furnace by (), in air atmosphere 400
ounder C condition, roasting 3 hr obtains carrier III;
(2) catalyst preparing
A () gets containing H
2pdCl
4and HAuCl
4aqueous solution 800ml be maceration extract B(palladium content: 2.75 g/L, gold content: 0.625 g/L), dipping 1000ml carrier III 3 hr obtains catalyst precarsor I;
B () is by 27.5g Na
2siO
39H
2o is made into the 100 ml aqueous solution and is added in above-mentioned catalyst precarsor I, and shake is for several times to avoid caking, and after leaving standstill 24 hr, under 80 DEG C of conditions, dry 8 hr obtain catalyst precarsor II;
C () at hydrogen atmosphere, (flow velocity is 0.2 ml/min, and temperature is 150 by catalyst precarsor II
oc) be down to room temperature after reductase 12 hr in and obtain catalyst precarsor III;
D () gets containing the KOAc aqueous solution 450 ml is maceration extract (KOAc:0.1 g/ml), and impregnated catalyst precursor II I 3 hr, in 105
ounder C condition, dry 6 hr obtain finished catalyst;
The main preparation condition of catalyst lists in table 1.
(3) physical property characterizes
Use inductively coupled plasma spectrum generator (ICP) to measure Pd, Au, K content in finished catalyst, in catalyst, F constituent content is by solid-state nuclear magnetic resonance F spectrometry.The physical property of catalyst lists in table 2.
(4) catalyst performance evaluation
Use fixed bed reactors evaluation, actual conditions is:
Catalyst packing volume: 700 ml;
Reaction raw materials composition (in mole hundred parts of ratios): oxygen: ethene: nitrogen: acetic acid=1:7:8:2;
Raw material volume air speed: 3000 hr
-1;
Reaction pressure: 8.0 atm;
Reaction temperature: 200
oc;
Reaction time: 500 hr;
With the content of each component in gas chromatography analytical reactions product, then calculate the space time yield of catalyst and selective.
Table 2 lists space time yield and the selective data of catalyst.
[comparative example 1]
(1) catalyst preparing
A () gets containing H
2pdCl
4and HAuCl
4aqueous solution 800ml be maceration extract B(palladium content: 2.75 g/L, gold content: 0.625 g/L), dipping 1000ml carrier III 3 hr obtains catalyst precarsor I;
B () is by 27.5g Na
2siO
39H
2o is made into the 100 ml aqueous solution and is added in above-mentioned catalyst precarsor I, and shake is for several times to avoid caking, and after leaving standstill 24 hr, under 80 DEG C of conditions, dry 8 hr obtain catalyst precarsor II;
C () at hydrogen atmosphere, (flow velocity is 0.2 ml/min, and temperature is 150 by catalyst precarsor II
oc) be down to room temperature after reductase 12 hr in and obtain catalyst precarsor III;
D () gets containing the KOAc aqueous solution 450 ml is maceration extract (KOAc:0.1 g/ml), and impregnated catalyst precursor II I 3 hr, in 105
ounder C condition, dry 6 hr obtain finished catalyst;
The main preparation condition of catalyst lists in table 1.
(2) physical property characterizes
Use inductively coupled plasma spectrum generator (ICP) to measure Pd, Au, K content in finished catalyst, in catalyst, F constituent content is by solid-state nuclear magnetic resonance F spectrometry.The physical property of catalyst lists in table 2.
(3) catalyst performance evaluation
Use fixed bed reactors evaluation, actual conditions is:
Catalyst packing volume: 700 ml;
Reaction raw materials composition (in mole hundred parts of ratios): oxygen: ethene: nitrogen: acetic acid=1:5.25:5:1.2;
Raw material volume air speed: 2000 hr
-1;
Reaction pressure: 7.0 atm;
Reaction temperature: 150
oc;
Reaction time: 500 hr;
With the content of each component in gas chromatography analytical reactions product, then calculate the space time yield of catalyst and selective.
Table 2 lists space time yield and the selective data of catalyst.
[comparative example 2]
(1) carrier S iO
2pre-treatment
A () gets containing NaF and NH
4f mixed aqueous solution (n
f (NaF): n
f (NH4F)=1: 3) 800 ml are maceration extract A(F ion concentration: 3.0 g/L), flood preparing spherical SiO 2 carrier (BET specific surface 175 cm that 1000 ml diameters are 5.8 mm
2/ g, pore volume is 0.7 cm
3/ g) 3hr obtains catalyst precarsor I;
(b) by above-mentioned precursor carrier I in air dry oven, 105
ounder C condition, dry 4 hr obtain precursor carrier II;
C precursor carrier II is placed in Muffle furnace by (), in air atmosphere 400
ounder C condition, roasting 3 hr obtains carrier III;
(2) catalyst preparing
A () gets containing H
2pdCl
4and HAuCl
4aqueous solution 800ml be maceration extract B(palladium content: 2.75 g/L, gold content: 0.625 g/L), dipping 1000ml carrier III 3 hr obtains catalyst precarsor I;
B () is by 27.5g Na
2siO
39H
2o is made into the 100 ml aqueous solution and is added in above-mentioned catalyst precarsor I, and shake is for several times to avoid caking, and after leaving standstill 24 hr, under 80 DEG C of conditions, dry 8 hr obtain catalyst precarsor II;
C () at hydrogen atmosphere, (flow velocity is 0.2 ml/min, and temperature is 150 by catalyst precarsor II
oc) be down to room temperature after reductase 12 hr in and obtain catalyst precarsor III;
D () gets containing the KOAc aqueous solution 450 ml is maceration extract (KOAc:0.1 g/ml), and impregnated catalyst precursor II I 3 hr, in 105
ounder C condition, dry 6 hr obtain finished catalyst;
The main preparation condition of catalyst lists in table 1.
(3) physical property characterizes
Use inductively coupled plasma spectrum generator (ICP) to measure Pd, Au, K content in finished catalyst, in catalyst, F constituent content is by solid-state nuclear magnetic resonance F spectrometry.The physical property of catalyst lists in table 2.
(4) catalyst performance evaluation
Use fixed bed reactors evaluation, actual conditions is:
Catalyst packing volume: 700 ml;
Reaction raw materials composition (in mole hundred parts of ratios): oxygen: ethene: nitrogen: acetic acid=1:5.25:5:1.2;
Raw material volume air speed: 2000 hr
-1;
Reaction pressure: 7.0 atm;
Reaction temperature: 150
oc;
Reaction time: 500 hr;
With the content of each component in gas chromatography analytical reactions product, then calculate the space time yield of catalyst and selective.
Table 2 lists space time yield and the selective data of catalyst.
Table 1 catalyst preparation conditions
Content of fluoride ion in maceration extract A, g/L | Fluoride kind and with the ratio of the salt of the molar ratio computing hydrofluoric acid of fluorine element with hydrofluoric acid in maceration extract | Palladium content in maceration extract, g/L | Gold content in maceration extract, g/L | Potassium content in maceration extract, g/L | |
Embodiment 1 | 3.0 | NH 4F | 2.75 | 0.625 | 100 |
Embodiment 2 | 3.0 | (NH 4) 3SiF 6 | 2.75 | 0.625 | 100 |
Embodiment 3 | 3.0 | NaF | 2.75 | 0.625 | 100 |
Embodiment 4 | 3.0 | KF | 2.75 | 0.625 | 100 |
Embodiment 5 | 3.0 | n F(NH4F) : n F(HF) = 1 : 0.5 | 2.75 | 0.625 | 100 |
Embodiment 6 | 3.0 | n F(NH4F) : n F(HF) = 1 : 1 | 2.75 | 0.625 | 100 |
Embodiment 7 | 3.0 | n F(NH4F) : n F(HF) = 1 : 2 | 2.75 | 0.625 | 100 |
Embodiment 8 | 3.0 | n F(NH4F) : n F(HF) = 1 : 3 | 2.75 | 0.625 | 100 |
Embodiment 9 | 3.0 | n F(NH4F) : n F(HF) = 1 : 4 | 2.75 | 0.625 | 100 |
Embodiment 10 | 3.0 | n F(NH4F) : n F(HF) = 1 : 5 | 2.75 | 0.625 | 100 |
Embodiment 11 | 3.0 | n F(NH4)3SiF6 : n F(HF)= 1 : 3 | 2.75 | 0.625 | 100 |
Embodiment 12 | 3.0 | n F(NaF) : n F(HF) = 1 : 3 | 2.75 | 0.625 | 100 |
Embodiment 13 | 3.0 | n F(KF) : n F(HF) = 1 : 3 | 2.75 | 0.625 | 100 |
Embodiment 14 | 0.5 | n F(NH4F) : n F(HF) = 1 : 3 | 2.75 | 0.625 | 100 |
Embodiment 15 | 5.0 | n F(NH4F) : n F(HF) = 1 : 3 | 2.75 | 0.625 | 100 |
Embodiment 16 | 3.0 | n F(NH4F) : n F(HF) = 1 : 3 | 0.95 | 0.5 | 100 |
Embodiment 17 | 3.0 | n F(NH4F) : n F(HF) = 1 : 3 | 11.5 | 10.0 | 100 |
Comparative example 1 | --- | 2.75 | 0.625 | 100 | |
Comparative example 2 | 3.0 | n F(NaF) : n F(NH4F) = 1 : 3 | 2.75 | 0.625 | 100 |
2(is continued for table) catalyst physical property and evaluating data
Palladium content, g/L | Gold content, g/L | Potassium content, g/L | Oil repellent, g/L | Reaction temperature ( oC) | |
Embodiment 1 | 3.0 | 0.63 | 30 | 3.0 | 150 |
Embodiment 2 | 3.0 | 0.64 | 30 | 3.0 | 150 |
Embodiment 3 | 3.0 | 0.64 | 30 | 3.0 | 150 |
Embodiment 4 | 3.0 | 0.64 | 30 | 3.0 | 150 |
Embodiment 5 | 3.0 | 0.64 | 30 | 3.0 | 150 |
Embodiment 6 | 3.0 | 0.64 | 30 | 3.0 | 150 |
Embodiment 7 | 3.0 | 0.64 | 30 | 3.0 | 150 |
Embodiment 8 | 3.0 | 0.64 | 30 | 3.0 | 150 |
Embodiment 9 | 3.0 | 0.64 | 30 | 3.0 | 150 |
Embodiment 10 | 3.0 | 0.64 | 30 | 3.0 | 150 |
Embodiment 11 | 3.0 | 0.64 | 30 | 3.0 | 150 |
Embodiment 12 | 3.0 | 0.64 | 30 | 3.0 | 150 |
Embodiment 13 | 3.0 | 0.64 | 30 | 3.0 | 150 |
Embodiment 14 | 3.0 | 0.64 | 30 | 0.5 | 130 |
Embodiment 15 | 3.0 | 0.64 | 30 | 5.0 | 165 |
Embodiment 16 | 1.0 | 0.10 | 30 | 3.0 | 180 |
Embodiment 17 | 12.0 | 9.0 | 30 | 3.0 | 200 |
Comparative example 1 | 3.0 | 0.64 | 30 | 3.0 | 150 |
Comparative example 2 | 3.0 | 0.64 | 30 | 3.0 | 150 |
Table 2(continues) catalyst physical property and evaluating data
Claims (10)
1. for the catalyst of ethylene process vinyl acetate synthesis, described catalyst comprises active component, co-catalyst and carrier, described active component is Pd, Au and alloy thereof, co-catalyst is potassium acetate, in wherein said catalyst, Pd content is 1.0-12 g/L, Au content is 0.1-9.0 g/L, and described cocatalyst content is 10 ~ 50 g/L; It is characterized in that the carrier of described catalyst is a kind of SiO of fluorochemical modification
2.
2. catalyst as claimed in claim 1, is characterized in that Oil repellent 0.5 – 5.0 g/L in described catalyst.
3. catalyst as claimed in claim 1, is characterized in that described fluorochemical is at least one in the salt of hydrofluoric acid and hydrofluoric acid, fluosilicate.
4. catalyst as claimed in claim 3, is characterized in that described fluorochemical is the mixture that the salt of hydrofluoric acid and hydrofluoric acid forms.
5. catalyst as claimed in claim 3, is characterized in that the salt of described hydrofluoric acid is at least one in the alkali metal salt of the ammonium salt of hydrofluoric acid, hydrofluoric acid.
6. catalyst as claimed in claim 4, is characterized in that the alkali metal salt of described hydrofluoric acid is at least one in NaF, KF.
7. catalyst as claimed in claim 4, is characterized in that the salt of hydrofluoric acid described in the molar ratio computing with fluorine element is 1 with the ratio of hydrofluoric acid: (0.1 ~ 10).
8. catalyst as claimed in claim 1, is characterized in that described carrier B ET specific area is 150-200 cm
2/ g, pore volume is 0.6 ~ 0.8 cm
3/ g.
9. the preparation method of catalyst described in any one of claim 1 ~ 8, comprises the following steps:
A aequum water-soluble fluorine-containing compound is dissolved in the aqueous solution and makes maceration extract A by (), adopt infusion process, the carrier silica gel of aequum and maceration extract are mixed to get precursor carrier I;
B (), by dry after precursor carrier I, obtains precursor carrier II;
C precursor carrier II is obtained carrier III after roasting by () under air atmosphere condition;
D aequum palladium, gold compound are dissolved in solvent and make maceration extract B by (), the carrier III of aequum and maceration extract B is mixed to get catalyst precarsor I;
E aequum alkali metal silicate solutions mixes with above-mentioned catalyst precarsor I by () makes described palladium, gold compound is converted into sedimentation type, obtains catalyst precarsor II;
F (), by reducing agent reducing catalyst precursor II, obtains catalyst precarsor III;
G the co-catalyst potassium acetate of aequum is dissolved in pure water and makes maceration extract C by (), mixed by the catalyst precarsor III of aequum with maceration extract C, and drying dewaters to obtain described catalyst.
10. the method for vinyl acetate synthesis, under such as catalyst according to any one of claim 1 ~ 8 exists, oxygen is consisted of: ethene: nitrogen: acetic acid=1: 5 ~ 7: 4 ~ 8: 1 ~ 2 with molar ratio computing raw material, reaction pressure is 6.0 ~ 8.0 atm, reaction temperature is 130 ~ 200 DEG C, and raw material volume air speed is 1600 ~ 3000 h
-1.
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CN107282137A (en) * | 2016-04-12 | 2017-10-24 | 中国石油化工股份有限公司 | The method for preparing catalyst of vinyl acetate |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1998052688A1 (en) * | 1997-05-22 | 1998-11-26 | Celanese Gmbh | Method for producing vinyl acetate |
CN1432431A (en) * | 2002-01-15 | 2003-07-30 | 北京燕山石油化工公司研究院 | Catalyst for cracking ether to prepare tert-olefine and its prepn and application |
CN101147878A (en) * | 2006-09-20 | 2008-03-26 | 中国石油化工股份有限公司 | Catalyst for preparing vinyl acetate |
CN101884920A (en) * | 2009-05-13 | 2010-11-17 | 中国石油化工股份有限公司 | Preparation method for fluid catalyst used for preparing vinyl acetate |
CN102861575A (en) * | 2011-07-07 | 2013-01-09 | 中国石油化工股份有限公司 | Shell catalyst and preparation method thereof |
CN103120958A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Vinyl acetate catalyst and preparation method thereof |
-
2013
- 2013-09-24 CN CN201310435312.0A patent/CN104437624B/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1998052688A1 (en) * | 1997-05-22 | 1998-11-26 | Celanese Gmbh | Method for producing vinyl acetate |
CN1432431A (en) * | 2002-01-15 | 2003-07-30 | 北京燕山石油化工公司研究院 | Catalyst for cracking ether to prepare tert-olefine and its prepn and application |
CN101147878A (en) * | 2006-09-20 | 2008-03-26 | 中国石油化工股份有限公司 | Catalyst for preparing vinyl acetate |
CN101884920A (en) * | 2009-05-13 | 2010-11-17 | 中国石油化工股份有限公司 | Preparation method for fluid catalyst used for preparing vinyl acetate |
CN102861575A (en) * | 2011-07-07 | 2013-01-09 | 中国石油化工股份有限公司 | Shell catalyst and preparation method thereof |
CN103120958A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Vinyl acetate catalyst and preparation method thereof |
Non-Patent Citations (2)
Title |
---|
LI XIAOFEI 等: "Pd nanoparticles confined in fluoro‐functionalized yolk‐shell‐structured silica for olefin hydrogenation in water", 《CHINESE JOURNAL OF CATALYSIS》 * |
李倩 等: "乙烯气相法制醋酸乙烯钯金催化剂的研究进展", 《分子催化》 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107282137A (en) * | 2016-04-12 | 2017-10-24 | 中国石油化工股份有限公司 | The method for preparing catalyst of vinyl acetate |
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